Thin film fluopolymer composite cmp polishing method

ABSTRACT

The invention provides a polymer-polymer composite polishing method comprising a polishing layer having a polishing surface for polishing or planarizing a substrate. The method includes attaching a polymer-polymer composite having a polishing layer and a polymeric matrix. The polymer matrix has fluoropolymer particles embedded in the polymeric matrix. Then a cationic particle slurry is applied to the polymer-polymer composite polishing pad. Conditioning the polymer-polymer composite polishing pad with an abrasive cuts the polymer-polymer composite polishing pad; and rubbing the cut polymer-polymer composite polishing pad against the substrate forms the polishing surface. The polishing surface has a fluorine concentration measured in atomic percent at a penetration depth of 1 to 10 nm of at least ten percent higher than the bulk fluorine concentration measured with at a penetration depth of 1 to 10 μm to polish or planarize the substrate.

BACKGROUND OF THE INVENTION

Chemical Mechanical Planarization (CMP) is a variation of a polishingprocess that is widely used to flatten, or planarize, the layers ofconstruction of an integrated circuit in order to precisely buildmultilayer three dimensional circuitry. The layer to be polished istypically a thin film (less than 10,000 Angstroms) that has beendeposited on an underlying substrate. The objectives of CMP are toremove excess material on the wafer surface to produce an extremely flatlayer of a uniform thickness, the uniformity extending across the entirewafer. Control of removal rate and the uniformity of removal are ofparamount importance.

CMP utilizes a liquid, often called slurry, which contains nano-sizedparticles. This is fed onto the surface of a rotating multilayer polymersheet, or pad, which is mounted on a rotating platen. Wafers are mountedinto a separate fixture, or carrier, which has a separate means ofrotation, and pressed against the surface of the pad under a controlledload. This leads to a high rate of relative motion between the wafer andthe polishing pad (i.e., there is a high rate of shear at both thesubstrate and the pad surface. Slurry particles trapped at the pad/waferjunction abrade the wafer surface, leading to removal. In order tocontrol rate, prevent hydroplaning, and to efficiently convey slurryunder the wafer, various types of texture are incorporated into theupper surface of the polishing pad. Fine-scale texture is produced byabrading the pad with an array of fine diamonds. This is done to controland increase removal rate, and is commonly referred to as conditioning.Larger scale grooves of various patterns and dimensions (e.g., XY,circular, radial) are also incorporated for slurry transport regulation.

Removal rate during CMP is widely observed to follow the PrestonEquation, Rate=K_(p)*P*V, where P is pressure, V is velocity, and K_(p)is the so-called Preston Coefficient. The Preston Coefficient is alumped sum constant that is characteristic of the consumable set beingused. Several of the most important effects contributing to K_(p) areprovided as follows:

-   -   (a) pad contact area (largely derived from pad texture and        surface mechanical properties);    -   (b) the concentration of slurry particles on the contact area        surface available to do work; and    -   (c) the reaction rate between the surface particles and the        surface of the layer to be polished.

Effect (a) is largely determined by pad properties and the conditioningprocess. Effect (b) is determined by both pad and slurry, while effect(c) is largely determined by slurry properties.

The advent of high capacity multiple layer memory devices (e.g., 3D NANDflash memory) has led to a need for further increases in removal rate.The critical part of the 3D NAND manufacturing process consists ofbuilding up multilayer stacks of SiO₂ and Si₃N₄ films in an alternatingfashion in a pyramidal staircase fashion. Once completed, the stack iscapped with a thick SiO₂ overlayer, which must be planarized prior tocompletion of the device structure. This thick film is commonly referredto as the pre-metal dielectric (PMD). The device capacity isproportional to the number of layers in the layered stack. Currentcommercial devices use 32 and 64 layers, and the industry is rapidlymoving to 128 layers. The thickness of each oxide/nitride pair in thestack is ˜125 nm. Thus the thickness of the stack increases directlywith the number of layers (32=4,000 nm, 64=8,000 nm, 128=16,000 nm). Forthe PMD step, the total amount of capping dielectric to be removed isapproximately equal to ˜1.5 times the stack thickness, assuming aconformal deposition of the PMD.

Conventional dielectric CMP slurries have removal rates of ˜250 nm/min.This yields undesirably lengthy CMP process times for the PMD step,which now is the primary bottleneck in the 3D NAND manufacturingprocess. Consequently, there has been much work on developing faster CMPprocesses. Most improvements have focused on process conditions (higherP and V), changing the pad conditioning process, and improvements inslurry design, particularly in ceria-based slurries. If an improved padcould be developed that can be paired with the existing processes andceria slurries to achieve higher removal rate without introducing anynegative effects, it would constitute a significant improvement in CMPtechnology.

Hattori et al (Proc. ISET07, p. 953-4 (2007)) discloses comparative zetapotential vs. pH plots for various lanthanide particle dispersions,including ceria. The pH of zero charge (often termed the isoelectric pH)was measured as ˜6.6. Below this pH, the particle has a positivepotential; above this pH the particle has a negative potential. Forinorganic particles, such as silica and ceria, the isoelectric pH andthe surface charge at pH above and below the isoelectric pH aredetermined by the acid/base equilibrium of the surface hydroxyl groups.

For the case of polishing dielectrics with commercial ceria slurries andconventional pads, the electrostatic attraction between the particle andpad gives rise to a characteristic rate dependence on particleconcentration in the slurry. As discussed by Li et al (Proceedings of2015 Intl. Conf. on Planarization, Chandler, Ariz., p. 273-27 (2015))the concentration dependence of colloidal ceria particle on dielectricpolishing rates at pH below the isoelectric pH of the slurry showssaturation behavior at very low particle concentration (˜1%). Above thisconcentration, addition of more particles has no effect on polishingrate. For systems where the particle/pad interactions are repulsive, nosuch saturation behavior is seen. The economic benefits of low particleconcentration ceria slurries for dielectric polishing have been a majordriving force for its commercial use, despite its relatively higherprice.

For dielectric CMP using silica-based slurries, the majority of theslurries used are alkaline, typically at pH 10 or higher. Since thesilica particles have an isoelectric pH of ˜2.2; the consequence is thatthey have a high negative charge at the slurry pH.

Prior art pad design has largely neglected pad polymer modification as ameans to achieving increased rates. The primary methods used to achieveincreased rate in CMP pads are as follows:

-   -   a) optimization of groove design without changing the        composition of the top pad layer;    -   b) alter the conditioning process without changing the        composition of the top pad layer;    -   c) provide pads with more desirable conditioning response by        changing the conditioning response of the top pad layer; and    -   d) provide pads with top pad layers having higher hardness or        modified elastic properties.

Despite all these solutions, there remains a need to develop planarizingpolishing pads that increase removal rate without a significant increasein polishing defects for polishing with both anionic and cationicparticle slurries.

STATEMENT OF THE INVENTION

An embodiment of the invention provides a method for polishing orplanarizing a substrate of at least one of semiconductor, optical andmagnetic substrates, the method comprising the following: attaching apolymer-polymer composite polishing pad to a polishing device, thepolymer-polymer composite polishing pad comprising a polishing layerhaving a polishing surface for polishing or planarizing the substrate; apolymeric matrix forming the polishing layer, the polymer matrix havinga tensile strength, and fluoropolymer particles embedded in thepolymeric matrix, the fluoropolymer particles having a tensile strengthlower than the tensile strength of the polymeric matrix; applying aslurry to the polymer-polymer composite polishing pad, the slurrycontaining cationic particles; conditioning the polymer-polymercomposite polishing pad with an abrasive to cut the polymer-polymercomposite polishing pad; and rubbing the cut polymer-polymer compositepolishing pad against the substrate to form the polishing surface havinga fluorine concentration measured by x-ray photoelectron spectroscopy inatomic percent at a penetration depth of 1 to 10 nm of at least tenpercent higher than the bulk fluorine concentration measured withenergy-dispersion X-ray spectroscopy at a penetration depth of 1 to 10μm and to polish or planarize the substrate with the thin film on thepolishing surface.

Another embodiment of the invention provides a method for polishing orplanarizing a substrate of at least one of semiconductor, optical andmagnetic substrates, the method comprising the following: attaching apolymer-polymer composite polishing pad to a polishing device, thepolymer-polymer composite polishing pad comprising a polishing layerhaving a polishing surface for polishing or planarizing the substrate, apolymeric matrix forming the polishing layer, the polymer matrix havinga tensile strength, and fluoropolymer embedded in the polymeric matrixthe fluoropolymer particles having a tensile strength lower than thetensile strength of the polymeric matrix; applying a slurry to thepolymer-polymer composite polishing pad, the slurry containing cationicparticles, the slurry including cationic particles; conditioning thepolymer-polymer composite polishing pad with an abrasive to cut thepolymer-polymer composite polishing pad; and rubbing the cutpolymer-polymer composite polishing pad against the substrate to formthe polishing surface having a fluorine concentration measured by x-rayphotoelectron spectroscopy in atomic percent at a penetration depth of 1to 10 nm of at least twenty percent higher than the bulk fluorineconcentration measured with energy-dispersion X-ray spectroscopy at apenetration depth of 1 to 10 μm and to polish or planarize the substratewith the thin film on the polishing surface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of contact angle versus percent PTFE addition for apolyurethane polishing pad.

FIG. 2 is measurement of coefficient of friction data for ahigh-strength polyurethane polishing pad versus a PTFE containingversion as generated with a colloidal-silica slurry and acolloidal-ceria slurry.

FIG. 3 is a plot of conditioner debris size for a high-strengthpolyurethane polishing pad versus that obtained with PFA and PTFEadditions.

FIG. 4 is a QCM plot showing interaction between PFA and PTFE particlesand a ceria crystal.

FIG. 5A is a plot of TEOS removal rate in A/min. for a soft polyurethanepolishing pad without a PTFE particle additions.

FIG. 5B is a plot of TEOS removal rate in A/min. for a soft polyurethanepolishing pad with a PTFE particle additions.

FIG. 6 is a plot of surface roughness for a soft polyurethane polishingpad with and without a PTFE particle addition.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides a polymer-polymer composite polishing pad usefulfor polishing or planarizing a substrate of at least one ofsemiconductor, optical and magnetic substrates. The invention hasparticular value for planarizing patterned silicon wafers with slurriescontaining cationic abrasive particles. A key element of the presentinvention is the modification of the top pad surface properties tofacilitate enhanced adsorption of slurry particles onto the uppersurface through the incorporation of fluoropolymer particles into thepolishing pad's matrix. An unexpected and novel effect in pads of thepresent invention, is that the addition of low tensile strengthfluoropolymer particles in relatively low concentration of approximately1 to 20 wt % of the total polymer concentration) yields improved removalrate and desirably highly negative or positive surface zeta potential.Unless specifically noted otherwise, this specification provides allconcentrations in weight percent. Typically, the zeta potential of thefluoropolymer is more negative than the matrix as measured in distilledwater at a pH of 7. This increase in negativity can facilitatepreferential attraction of positively charged particles to polishingasperities located at the polishing surface of the polishing pad duringpolishing. For purposes of this specification, positively chargedparticles include cationic particles such as ceria, titania, nitrogendoped silica, aminosilane-coated silica and particles modified withcationic surfactants. In particular, the fluoropolymer-modified pads arequite effective for polishing with ceria-containing slurries. Thepolishing surface is hydrophilic as measured with distilled water at apH of 7 at a surface roughness of 10 μm rms after soaking in distilledwater for five minutes. For example, at a pH of 7, polyurethane willgenerally have a zeta potential in the range of −5 mV to −15 mV. Thezeta potential of polyurethane is typically positive at low pH levelsand becomes negative with increasing pH levels. Most fluoropolymerparticles, however, are hydrophobic and have a zeta potential of −20 mVto −50 mV at pH 7. The zeta potential of the fluoropolymers tend to haveless variation with change in pH level than polyurethane.

During polishing, conditioners, such as diamond conditioning disks cutthe polishing pad to expose fresh fluoropolymer to the surface. Aportion of this fluoropolymer extends upward to form raised surfaceareas on the polishing pad. Then the wafer rubs against thefluoropolymer to form a thin film on the polishing pad surface. Thisfilm tends to be rather thin, such as ten or less atom layers thick.These thin films are so thin that they are typically not visible withstandard scanning electron microscopes. The fluorine concentration ofthis film, however, is visible by x-ray photoelectron spectroscopyinstruments. This instrument can measure fluorine and carbonconcentrations with a penetration depth of 1 to 10 nm. It is criticalthat this film only cover a portion of the polishing surface. If thefluoropolymer film covers the entire surface, then the polishing padremains hydrophobic during polishing. Unfortunately, these hydrophobicpads tend to provide inefficient polishing removal rates. Furthermore itis critical that the polymer matrix maintains sufficient mechanicalintegrity in order that it can facilitate the smearing of thefluoropolymer onto the polymer matrix. For example and mostadvantageously, slicing the polishing pad below the polishing surfaceand parallel to the polishing layer leaves one end of the fluoropolymerparticles anchored in the polymeric matrix while the other end canplastically deform at least 100% in elongation.

The polishing surface must include sufficient matrix polymer at thepolishing surface to wet the pad during polishing. This hydrophilicinteraction between the polishing pad and the slurry is important formaintaining efficient slurry distribution and polishing. For purposes ofthis specification, hydrophilic polishing surface refers to a polishingpad with a surface roughness of 10 μm rms after soaking in distilledwater (pH 7) for five minutes. Diamond conditioning creates the surfacetexture. Under some circumstances, it is possible to simulate diamondconditioning with an abrasive cloth, such as sand paper. Typically, thefluoropolymer film covers 20 to 80 percent of the polishing pad surface.A comparison between fluorine concentration as measured with an X-rayphotoelectron spectroscopy and deeper penetrating energy-dispersionX-ray spectroscopy at a penetration depth of 1 to 10 μm providesconclusive evidence of this film. The pads can generate a fluorineconcentration at least ten atomic percent higher measured at apenetration depth of 1 to 10 nm than in the bulk of the matrix measuredat a penetration depth of 1 to 10 μm. Preferably, the pads can generatea fluorine concentration at least twenty atomic percent higher measuredat a penetration depth of 1 to 10 nm than in the bulk of the matrixmeasured at a penetration depth of 1 to 10 μm.

Moreover, another unanticipated effect of the addition of low tensilestrength fluoropolymers in relatively low concentration of approximately1 to 20 wt % of the total polymer concentration) is that it results in asignificant reduction in the size of the pad conditioning debris. Thefluoropolymer particles, however, can function effectively when theycomprise 2 to 30 volume percent of the polymer-polymer composite pad.This is believed to be a factor in the reduction in defectivityobserved. Yet another unexpected and novel effect in pads of the presentinvention is that the surface zeta potential of the pad may be modifiedby changing the particular fluoropolymer added to the parent polymer.This allows the pad to produce enhanced polishing rates for multipletypes of slurries while maintaining the desirably low sizes of padconditioning debris, thus improving defect levels, and maintaining thedesirable properties of the parent pad with respect to planarization. Inaddition, the negative zeta potential can help stabilize the slurry tolimit detrimental particle precipitation that can result in detrimentalwafer scratching. Thus, this limiting of particle precipitation canoften result in lower polishing defects.

The addition of fluoropolymer particles to a parent polymer, such as apolyurethane block copolymer forms a multipolymer composite. Preferably,the matrix is a polyurethane block copolymer containing hard and softsegments. Unlike many other materials, fluoropolymers do not form bondsor linkages to the polyurethane matrix, but exist as a separate polymeror phase. This matrix can be either porous or non-porous. It ispreferred that the fluoropolymers are significantly softer and moremalleable than the surrounding matrix. It has been discovered that thislow tensile strength allows the fluoropolymer to smear and form a thinfilm covering the matrix. The low tensile strength in combination withthe smearing is critical to achieving excellent polishing results.Furthermore, the fluoropolymer addition weakens the polishing pad, butdecreases the amount of 1 to 10 μm debris particles formed duringpolishing. When added in small amounts (1-20% by weight) the resultingmaterial still has mechanical properties suitable for use as a polishingpad. But the response to the pad conditioning process is quitedifferent. In fact, the fluoropolymer is capable of 100% elongation whentrapped at one end in the polishing matrix. These fluoropolymers tend tofill in gaps between surface asperities and reduce surface roughness.

Fluorinated polymer particles (PTFE, PFA) when used as powder incommercial pad formulations show improvement in defects and polishingremoval rate when polishing semiconductor substrates with cationicabrasives. The chemical structures of acceptable fluorinated additivesare below as follows:

-   -   (a) PTFE (polytetrafluoroethylene)

-   -   (b) PFA (Copolymer of tetrafluoroethylene (TFE) and        perfluoroalkylvinylethers (PFAVE))

-   -   (c) FEP (Copolymer of tetrafluoroethylene (TFE) and        hexafluoropropylene (HFP))

-   -   (d) PVF (polyvinylfluoride)

Additional acceptable examples of fluoropolymers are ETFE (ethylenetetrafluoroethylene), PVDF (polyvinylidene fluoride) and ECTFE (ethylenechlorotrifluoroethylene). Preferably, the fluoropolymer is selected fromPTFE, PFA, FEP, PVF, ETFE, ECTFE and combinations thereof.

Many hydrophobic hydrocarbon polymers such as fluorine end-cappedpolytetrafluoroethylene (PTFE) have highly negative zeta potentials inwater, typically less than −20 mV, and are quite hydrophobic, withstatic water contact angles of above 100 degrees. However, the contactangle hysteresis is extremely low. Typical advancing, static, andreceding contact angles in water are 110°, 110°, and 95° respectively,i.e., the material surface remains highly hydrophobic. The explanationfor the highly negative zeta potential of PTFE is simply that it is dueto the high degree of orientation of the water dipole at the polymersurface together with the low surface polarity. Other hydrophobicfluoropolymers, such as polyvinylfluoride (PVF) have similar staticwater contact angles, but can have high positive zeta potentials inwater, typically greater than +30 mV. PVF differs from PTFE in that itis much more polar. The positive zeta potential is due to the presenceof nitrogen containing polymerization initiators that break apart andend cap the fluoropolymers. For example azo initiators can form cationicfluoropolymer particles for multiple fluoropolymers, including PTFE,PFA, FEP, PVF, ETFE, ECTFE and combinations thereof. Most preferably,the cationic fluoropolymer is PVF.

In the conditioning process, diamond crystals embedded in a metal orceramic matrix act as cutting tools, cutting into the pad and removingmaterial to form a resulting surface texture. There are two basic modesof diamond conditioning interaction, plastic deformation, and fracture.While the type, size, and number of diamond particles per unit area canhave an effect, the polishing pad structure has a much bigger impact onthe mode of material removal. At one extreme, a solid high toughnesspolymer is expected to result in a largely plastic mode of conditioningwear, producing furrows but not necessarily removing mass. At the otherextreme, a brittle glassy polymer will favor pad removal via fracture,causing large chunks of the pad surface to be released into the slurry.For polymer composites or polymer foams, the volume fraction of the voidor additive tends to shift the conditioning mode toward fracture, asfewer pad polymer bonds need to be broken to release a volume roughlyequivalent to the interstitial space between said voids or second phase.For the closed cell polyurethane foams currently used in CMP pads, thesizes of these fracture fragments are quite large, typically tens ofmicrons in size. Since these pads are relatively hard polymers,particles in this size range have been shown to cause scratching damageto the wafers being polished if they are trapped in the slurry filmunder pressure during CMP. For pads of the current invention, theaddition of the fluoropolymer particles, especially for small diameters,markedly reduces the size of the conditioning debris, as they act tofurther weaken the tensile strength of the material in the interstitialspace between cellular voids. This contributes to a reduction in thescratch density during polishing.

When the fluoropolymer particles in pads of the present invention areexposed at the pad surface during polishing, the high shear rate arisingfrom the relative motion of the pad and wafer, together with the lowshear strength of the fluoropolymer particles, results in plastic flowof the fluoropolymer onto the adjacent portions of the pad surface. Overtime, this results in a thin discontinuous fluoropolymer film on thewafer surface. At low levels of particle addition, this results in aheterogeneous surface consisting of urethane-rich and fluoropolymer-richzones. Polishing pads with this type of heterogeneous surface have asignificant polishing rate enhancement for polishing withopposite-charged particles. The effective zeta potential of thisheterogeneous surface is controlled by the fluoropolymer used and therelative area of coverage. For example, use of PTFE particles, with anegative zeta potential, yields a pad surface with an enhanced negativezeta potential relative to the parent polymer.

In like fashion, the conditioning debris generated when pads of thepresent invention are used will also be attractive to slurry particles.Since these debris particles are small, adsorption of slurry particlesis expected to lead to the formation of slurry particle/pad particleagglomerates. Polishing operations that form these aggregates aremarkedly less harmful than in conventional pads for two reasons. First,since the parent debris is much smaller, the resulting agglomerates willalso be correspondingly smaller. Second, the agglomerates are expectedto have low binding strength due to the heterogeneous nature of theirsurface. Finally, the fluoropolymers can stabilize the slurry and slowparticle settling. This can be significant for ceria-containing andother cationic slurries. For example, the fluoropolymer particles have asettling sensitivity in the slurry containing cationic particles asfollows: a) determine settling slope in (%/hour) for the slurry; b)determine settling slope in (%/hour) for the slurry plus 0.1 wt %fluoropolymer particles; and c) slope a)-slope b) being ≥5%/hour.Because slurries only spend a limited amount of time on the polishingpad, a small change in slope can provide a significant decrease inpolishing defects.

Pads of the present invention may be used for a wide variety of slurriesto achieve enhanced polishing rate and reduced defectivity by the novelmeans of choosing the fluoropolymer additive to be incorporated andmatching it to the slurry particle and pH.

The CMP polishing pads in accordance with the present invention may bemade by methods comprising: providing the isocyanate terminated urethaneprepolymer; providing separately the curative component; and combiningthe isocyanate terminated urethane prepolymer and the curative componentto form a combination; to allowing the combination to react to form aproduct; forming a polishing layer from the product, such as by skivingthe product to form a polishing layer of a desired thickness andgrooving the polishing layer, such as by machining it; and, forming thechemical mechanical polishing pad with the polishing layer.

The isocyanate terminated urethane prepolymer used in the formation ofthe polishing layer of the chemical mechanical polishing pad of thepresent invention preferably comprises: a reaction product ofingredients, comprising: a polyfunctional isocyanate and a prepolymerpolyol mixture containing two or more components, one of which is afluoropolymer powder. The fluoropolymer powder does not react with theisocyanate. Rather, it is added to the prepolymer in order to create auniform dispersion prior to the final polymerization step.

The isocyanate terminated urethane prepolymer used in the formation ofthe polishing layer of the chemical mechanical polishing pad of thepresent invention preferably comprises: a reaction product ofingredients, comprising: a polyfunctional isocyanate and a prepolymerpolyol mixture containing two or more components, one of which is afluoropolymer powder. The fluoropolymer powder does not react with theisocyanate. Rather, it is added to the prepolymer in order to create auniform dispersion prior to the final polymerization step.

The invention works with a variety of polymer matrices, such aspolyurethane, polybutadiene, polyethylene, polystyrene, polypropylene,polyester, polyacrylamide, polyvinyl alcohol, polyvinyl chloridepolysulfone and polycarbonate. Preferably, the matrix is a polyurethane.For purposes of this specification, “polyurethanes” are products derivedfrom difunctional or polyfunctional isocyanates, e.g. polyetherureas,polyisocyanurates, polyurethanes, polyureas, polyurethaneureas,copolymers thereof and mixtures thereof. The CMP polishing pads inaccordance may be made by methods comprising: providing the isocyanateterminated urethane prepolymer; providing separately the curativecomponent; and combining the isocyanate terminated urethane prepolymerand the curative component to form a combination, then allowing thecombination to react to form a product. It is possible to form thepolishing layer by skiving a cast polyurethane cake to a desiredthickness and grooving or perforating the polishing layer. Optionally,preheating a cake mold with IR radiation, induction or direct electricalcurrent can reduce product variability when casting porous polyurethanematrices. Optionally, it is possible to use either thermoplastic orthermoset polymers. Most preferably, the polymer is a crosslinkedthermoset polymer.

Preferably, the polyfunctional isocyanate used in the formation of thepolishing layer of the chemical mechanical polishing pad of the presentinvention is selected from the group consisting of an aliphaticpolyfunctional isocyanate, an aromatic polyfunctional isocyanate and amixture thereof. More preferably, the polyfunctional isocyanate used inthe formation of the polishing layer of the chemical mechanicalpolishing pad of the present invention is a diisocyanate selected fromthe group consisting of 2,4-toluene diisocyanate; 2,6-toluenediisocyanate; 4,4′-diphenylmethane diisocyanate;naphthalene-1,5-diisocyanate; tolidine diisocyanate; para-phenylenediisocyanate; xylylene diisocyanate; isophorone diisocyanate;hexamethylene diisocyanate; 4,4′-dicyclohexylmethane diisocyanate;cyclohexanediisocyanate; and, mixtures thereof. Still more preferably,the polyfunctional isocyanate used in the formation of the polishinglayer of the chemical mechanical polishing pad of the present inventionis an isocyanate terminated urethane prepolymer formed by the reactionof a diisocyanate with a prepolymer polyol.

Preferably, the isocyanate-terminated urethane prepolymer used in theformation of the polishing layer of the chemical mechanical polishingpad of the present invention has 2 to 12 wt % unreacted isocyanate (NCO)groups. More preferably, the isocyanate-terminated urethane prepolymerused in the formation of the polishing layer of the chemical mechanicalpolishing pad of the present invention has 2 to 10 wt % (still morepreferably 4 to 8 wt %; most preferably 5 to 7 wt %) unreactedisocyanate (NCO) groups.

Preferably the prepolymer polyol used to form the polyfunctionalisocyanate terminated urethane prepolymer is selected from the groupconsisting of diols, polyols, polyol diols, copolymers thereof andmixtures thereof. More preferably, the prepolymer polyol is selectedfrom the group consisting of polyether polyols (e.g.,poly(oxytetramethylene)glycol, poly(oxypropylene)glycol and mixturesthereof); polycarbonate polyols; polyester polyols; polycaprolactonepolyols; mixtures thereof; and, mixtures thereof with one or more lowmolecular weight polyols selected from the group consisting of ethyleneglycol; 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol;1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol; neopentylglycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol;diethylene glycol; dipropylene glycol; and, tripropylene glycol. Stillmore preferably, the prepolymer polyol is selected from the groupconsisting of polytetramethylene ether glycol (PTMEG); ester basedpolyols (such as ethylene adipates, butylene adipates); polypropyleneether glycols (PPG); polycaprolactone polyols; copolymers thereof; and,mixtures thereof. Most preferably, the prepolymer polyol is selectedfrom the group consisting of PTMEG and PPG.

Preferably, when the prepolymer polyol is PTMEG, the isocyanateterminated urethane prepolymer has an unreacted isocyanate (NCO)concentration of 2 to 10 wt % (more preferably of 4 to 8 wt %; mostpreferably 6 to 7 wt %). Examples of commercially available PTMEG basedisocyanate terminated urethane prepolymers include Imuthane® prepolymers(available from COIM USA, Inc., such as, PET-80A, PET-85A, PET-90A,PET-93A, PET-95A, PET-60D, PET-70D, PET-75D); Adiprene® prepolymers(available from Chemtura, such as, LF 800A, LF 900A, LF 910A, LF 930A,LF 931A, LF 939A, LF 950A, LF 952A, LF 600D, LF 601D, LF 650D, LF 667,LF 700D, LF750D, LF751D, LF752D, LF753D and L325); Andur® prepolymers(available from Anderson Development Company, such as, 70APLF, 80APLF,85APLF, 90APLF, 95APLF, 60DPLF, 70APLF, 75APLF).

Preferably, when the prepolymer polyol is PPG, the isocyanate terminatedurethane prepolymer has an unreacted isocyanate (NCO) concentration of 3to 9 wt % (more preferably 4 to 8 wt %, most preferably 5 to 6 wt %).Examples of commercially available PPG based isocyanate terminatedurethane prepolymers include Imuthane® prepolymers (available from COIMUSA, Inc., such as, PPT-80A, PPT-90A, PPT-95A, PPT-65D, PPT-75D);Adiprene® prepolymers (available from Chemtura, such as, LFG 963A, LFG964A, LFG 740D); and, Andur® prepolymers (available from AndersonDevelopment Company, such as, 8000APLF, 9500APLF, 6500DPLF, 7501DPLF).

Preferably, the isocyanate terminated urethane prepolymer used in theformation of the polishing layer of the chemical mechanical polishingpad of the present invention is a low free isocyanate terminatedurethane prepolymer having less than 0.1 wt % free toluene diisocyanate(TDI) monomer content.

Non-TDI based isocyanate terminated urethane prepolymers can also beused. For example, isocyanate terminated urethane prepolymers includethose formed by the reaction of 4,4′-diphenylmethane diisocyanate (MDI)and polyols such as polytetramethylene glycol (PTMEG) with optionaldiols such as 1,4-butanediol (BDO) are acceptable. When such isocyanateterminated urethane prepolymers are used, the unreacted isocyanate (NCO)concentration is preferably 4 to 10 wt % (more preferably 4 to 10 wt %,most preferably 5 to 10 wt %). Examples of commercially availableisocyanate terminated urethane prepolymers in this category includeImuthane® prepolymers (available from COIM USA, Inc. such as 27-85A,27-90A, 27-95A); Andur® prepolymers (available from Anderson DevelopmentCompany, such as, IE75AP, IE80AP, IE 85AP, IE90AP, IE95AP, IE98AP); and,Vibrathane® prepolymers (available from Chemtura, such as, B625, B635,B821).

The polishing layer of the chemical mechanical polishing pad of thepresent invention may further contain a plurality of microelements.Preferably, the plurality of microelements are uniformly dispersedthroughout the polishing layer. Preferably, the plurality ofmicroelements is selected from entrapped gas bubbles, hollow corepolymeric materials, liquid filled hollow core polymeric materials,water soluble materials and an insoluble phase material (e.g., mineraloil). More preferably, the plurality of microelements is selected fromentrapped gas bubbles and hollow core polymeric materials uniformlydistributed throughout the polishing layer. Preferably, the plurality ofmicroelements has a weight average diameter of less than 150 μm (morepreferably of less than 50 μm; most preferably of 10 to 50 μm).Preferably, the plurality of microelements comprises polymericmicroballoons with shell walls of either polyacrylonitrile or apolyacrylonitrile copolymer (e.g., Expancel® microspheres from AkzoNobel). Preferably, the plurality of microelements is incorporated intothe polishing layer to at 0 to 50 vol. % porosity (Preferably 10 to 35vol. % porosity). The vol. % of porosity is determined by dividing thedifference between the specific gravity of an unfilled polishing layerand specific gravity of the microelement containing polishing layer bythe specific gravity of the unfilled polishing layer. Preferably, thefluoropolymer particles having an average particle size less than theaverage spacing of the polymeric microelements to improve particledistribution, reduce viscosity and facilitate casting.

The polishing layer of the CMP polishing pad of the present inventioncan be provided in both porous and nonporous (i.e., unfilled)configurations. Preferably, the polishing layer of the chemicalmechanical polishing pad of the present invention exhibits a density of0.4 to 1.15 g/cm³ (more preferably, 0.70 to 1.0; as measured accordingto ASTM D1622 (2014)).

Preferably, the polishing layer of the chemical mechanical polishing padof the present invention exhibits a Shore D hardness of 28 to 75 asmeasured according to ASTM D2240 (2015).

Preferably, the polishing layer has an average thickness of 20 to 150mils (510 to 3,800 μm). More preferably, the polishing layer has anaverage thickness of 30 to 125 mils (760 to 3200 μm). Still morepreferably 40 to 120 mils (1,000 to 3,000 μm); and most preferably 50 to100 mils (1300 to 2500 μm).

Preferably, the CMP polishing pad of the present invention is adapted tobe interfaced with a platen of a polishing machine. Preferably, the CMPpolishing pad is adapted to be affixed to the platen of a polishingmachine. Preferably, the CMP polishing pad can be affixed to the platenusing at least one of a pressure sensitive adhesive and vacuum.

The CMP polishing pad of the present invention optionally furthercomprises at least one additional layer interfaced with the polishinglayer. Preferably, the CMP polishing pad optionally further comprises acompressible base layer adhered to the polishing layer. The compressiblebase layer preferably improves conformance of the polishing layer to thesurface of the substrate being polished.

The CMP polishing pad of the present invention in its final form furthercomprises the incorporation of texture of one or more dimensions on itsupper surface. These may be classified by their size into macrotextureor microtexture. Common types of macrotexture employed for CMP controlhydrodynamic response and/or slurry transport, and include, withoutlimitation, grooves of many configurations and designs, such as annular,radial, and cross-hatchings. These may be formed via machining processesto a thin uniform sheet, or may be directly formed on the pad surfacevia a net shape molding process. Common types of microtexture are finerscale features that create a population of surface asperities that arethe points of contact with the substrate wafer where polishing occurs.Common types of microtexture include, without limitation, texture formedby abrasion with an array of hard particles, such as diamond (oftenreferred to as pad conditioning), either prior to, during or after use,and microtexture formed during the pad fabrication process.

An important step in substrate polishing operations is determining anendpoint to the process. One popular in situ method for endpointdetection involves providing a polishing pad with a window, which istransparent to select wavelengths of light. During polishing, a lightbeam is directed through the window to the substrate surface, where itreflects and passes back through the window to a detector (e.g., aspectrophotometer). Based on the return signal, properties of thesubstrate surface (e.g., the thickness of films thereon) can bedetermined for endpoint detection purposes. To facilitate such lightbased endpoint methods, the chemical mechanical polishing pad of thepresent invention, optionally further comprises an endpoint detectionwindow. Preferably, the endpoint detection window is selected from anintegral window incorporated into the polishing layer; and, a plug inplace endpoint detection window block incorporated into the chemicalmechanical polishing pad. For unfilled pads of the present inventionthat have sufficient transmittance, the upper pad layer itself can beused as the window aperture. If the polymer phase of pads of the presentinvention exhibit phase separation, a transparent region of the top padmaterial can also be produced by locally increasing the cooling rateduring fabrication to locally inhibit phase separation, resulting in amore transparent region suitable for use as the endpointing window.

CMP polishing pads are used in conjunction with a polishing slurry, asdescribed in the background of the invention. Pads of the presentinvention may be used for a wide variety of slurries to achieve enhancedpolishing rate and reduced defectivity by the novel means of choosingthe fluoropolymer additive to be incorporated and matching it to theslurry particle and pH.

CMP polishing pads of the present invention are designed for use withslurries whose pH is either above or below the isoelectric pH of theparticle being used. Maximum rate can be selected via the choice of thefluoropolymer based on simple criteria. For example, CeO₂ has anisoelectric pH of ˜6.5. Below this pH, the particle surface has a netpositive charge. Above this pH, the particle has a net negative charge.If the slurry pH is below the isoelectric pH of the slurry particle,then selection of a pad that contains a fluoropolymer particle additionthat has a negative zeta potential at that pH will produce the maximumimprovement in removal rate, e.g., PTFE or PFA. In like fashion, for aslurry using colloidal or fumed silica particles with a high pH (e.g.,10), maximum polishing rate will be achieved by selection of a pad whichcontains a fluoropolymer particle addition which has a positive zetapotential at that pH, i.e., PVF. This is a very attractive capability asit allows rate enhancement for virtually any slurry.

A significant novel advantage for pads of the present invention whenused with silica slurries is that, as described in the background of theinvention, the additional effect of the electrostatic attraction betweenthe inventive pad and the silica particles is the ability to affect asignificant reduction in the amount of particles used in the slurry toproduce polishing rate achieved with prior art pads. This providessignificant cost advantages to the user.

The CMP pads of the present invention may be manufactured by a varietyof processes that are compatible with thermoset urethanes. These includemixing the ingredients as described above and casting into a mold,annealed, and sliced into sheets of the desired thickness.Alternatively, they may be made in a more precise net shape form.Preferred processes in accordance with the present invention include: 1.thermoset injection molding (often referred to as “reaction injectionmolding” or “RIM′), 2. thermoplastic or thermoset injection blowmolding, 3. compression molding, or 4. any similar-type process in whicha flowable material is positioned and solidified, thereby creating atleast a portion of a pad's macrotexture or microtexture. In a preferredmolding embodiment of the present invention: 1. the flowable material isforced into or onto a structure or Substrate; 2. the Structure orSubstrate imparts a Surface texture into the material as it Solidifies,and 3. the Structure or Substrate is thereafter separated from theSolidified material.

Some embodiments of the present invention will now be described indetail in the following examples.

Examples: Sample Preparation

Samples of polishing pads, high-strength polyurethane (Sample A), mediumporosity polyurethane having an pore size of 40 μm (Sample B) andlow-porosity polyurethane having an pore size of 20 μm (Sample C), wereproduced with varying additions of four different commercialfluoropolymer powders, PTFE-1 (Chemours Zonyl™ MP-1000 particles),PTFE-2 (Chemours Zonyl™ MP-1200 particles), PFA (Solvay P-7010 copolymerof tetrafluoroethylene (TFE) and perfluoroalkylvinylethers (PFAVE)particles), and PVF (Nitrogen terminated polyvinyl fluoride particles)in the upper pad material. From manufacturer's data, the surfaceweighted mean particle sizes were MP-1000 1.6 μm, MP-1200—1.7 μm vs. 8.9μm for the PFA sample. The fluoropolymer powders were added to theprepolymer component of the polyurethane formulation prior to mixingwith the curative component and a gas or liquid filled polymericmicroelement component, present in the pads, to ensure a uniformdistribution in the final cured polyurethane. After preparation,equivalent pads with and without fluoropolymer particles were preparedand tested.

Example 1

The physical properties of a set of Sample A made with and without theaddition of 10 weight percent of PTFE-1 and PFA were conducted. As shownin the Table below, changes of note were the reduction in tensilestrength, hardness and the majority of the mechanical properties. Ofspecific interest was the difference in the effect of additions on theshear storage modulus (G′), which was characteristic of elastic behaviorversus the effect on the shear loss modulus (G″), which represents theamount of energy dissipated in the sample. Shear storage modulus G′ at40° C. showed a significant reduction relative to the control (−31% forPFA and −45% for PTFE). Shear loss modulus, G″ showed a similar trend(−26% for PFA and −37% for PTFE). While all samples were primarilyelastic polymers, tan 6, the ratio of G″ to G′, increased by 6% and 14%for PFA and PTFE additions, respectively. This was a direct measure ofthe increase in the energy dissipation effected by the fluoropolymeraddition. A similar trend was observed for tensile strength, whichdecreased by 6% for PFA addition and 14% for PTFE addition.

TABLE 1 Physical Property Comparison of High-Strength Polishing Padswith and without Fluoropolymer Particle Additions Tensile Young's ShoreD G′ G′ G″ Strength Modulus Toughness Pad Density, Hardness, at 30° C.at 40° C. at 40° C. G′ (30° C.)/ 23° C. 23° C. 23° C. Sample g/cm³ 2 sec(MPa) (MPa) (MPa) G′ (90° C.) (MPa) (MPa) (MPa) A 0.975 63.5 215.8 172.623.92 3.16 31.2 328.9 58.6 A-PFA 1.119 62.9 154.9 119.6 17.62 3.09 28.3315.3 58.2 A-PTFE 1.065 59.1 125.0 95.4 14.97 3.06 26.5 302.5 46.8

The data indicate that the fluoropolymer doped materials have decreasedphysical properties in relation to the parent material. This decrease inphysical properties indicated that the tensile strength of thefluoropolymer was less than that of the tensile strength of the matrixof Sample A. Tensile strength was measured in accordance with ASTM D412.

Microscopic analysis of the fluoropolymer doped pads revealed thepresence of discrete fluoropolymer particles, confirmed via EDSanalysis, which were randomly distributed within the polymer matrix. Thefluorocarbon particles showed no evidence of attraction to orinteraction with the flexible polymeric microelements that were alsopresent.

Example 2

The deionized water contact angle was measured on a set of mediumporosity polyurethane pads of Sample B that had varying amounts ofPTFE-2 added during manufacturing. As shown in FIG. 1, the contact angleincreased directly with increasing PTFE content to a steady state valueof around 140 degrees by 7.5% PTFE content. All pads with both PTFE andPFA additions were visibly more hydrophobic than the parent pad. Despitethis, the polishing surface is hydrophilic as measured with distilledwater at a pH of 7 at a surface roughness of 10 μm rms after soaking indistilled water for five minutes.

Example 3

A polishing test was performed on a set of high-strength Sample A padswith and without the addition of PTFE and PFA in order to demonstratethe beneficial effects of the present invention. The concentration ofeach fluoropolymer added was 8.1%. Three slurries were tested on eachpad set using 60 200 mm TEOS monitor wafers per test on an AppliedMaterials Mirra CMP polishing tool. The slurries used were two ceriaslurries (Asahi CES333F2.5 and DA Nano STI2100F) and a fumed silicaslurry (Cabot SS25). Conditions used were 3 psi (20.7 kPa) downforce, 93rpm platen speed, 87 rpm carrier speed, and 150 ml/minute slurry flow.Conditioners varied by slurry type. For the ceria slurries, a SaesolLPX-C4 diamond conditioner disk was used. For the silica slurry, aSaesol AK45 conditioner disk was used. All conditioners were usedconcurrently with polishing at 7 lb force (3.2 kgf). For each run, a padbreak-in conditioning step was used for 20 minutes at 7 lb force (3.2kgf) to ensure a uniform initial pad texture. Polishing removal rate anddefectivity summaries are shown below in Tables 2 and 2A. The polishingin Example 3 occurred at pH below the isoelectric point of ceria for theAsahi and DaNano slurries and a pH above the isoelectric point forsilica with SS25 slurry.

TABLE 2 PTFE -1 Additive Removal Rate (A/min) Average Scratch & Chattermarks 8.1 wt % Slurry Sample A- Sample A- Sample A- Sample A- SlurryType Control PTFE Comparison Control PTFE Comparison Asahi CES333F2.5Ceria 1,600 2,500 57% Higher 28 20 30% Lower DA Nano STI2100F Ceria1,040 1,200 15% Higher 38 22 40% Lower SS25 Silica 2,500 2,680 Similar28 32 12% Higher

TABLE 2A PFA Additive Removal Rate (A/min) Average Scratch & Chattermarks 8.1 wt % Slurry Sample A- Sample A- Sample A- Sample A- SlurryType Control PTFE Comparison Control PTFE Comparison Asahi CES333F2.5Ceria 2,029 2,268 12% Higher 20 10 50% Lower DA Nano STI2100F Ceria1,308 1,490 14% Higher 25 26 Similar SS25 Silica 2,559 2,614 Similar 3033 10% Higher

Polish rate increased substantially and defect levels, particularlyscratches and chattermarks, diminished substantially when thefluoropolymer particle-containing pads of the present invention wereused in conjunction with a cationic ceria-containing slurries. When ananionic silica-containing slurry was used, no such improvement resulted.This charge-specific response with ceria increasing rate and loweringdefects was unexpected.

In order to gain more insight into the observed improvements, severaltests were conducted. Comparison of post-polish pad roughness for theSample A with PFA additive showed reduced roughness relative to thecontrol (18% reduction in rms roughness as measured by a Nanofocus laserprofilometer). In addition, coefficient of friction (COF) measurementswere made during polishing with a ceria-containing slurry (CES333F2.5)and a silica-based slurry (Klebosol 1730) for the high-strength padswith and without the addition of 8.1 wt % PTFE. Polishing conditionswere the same as used for the tests described in Tables 2 and 2A. Asshown in FIG. 2, for the silica slurry, no significant difference in COFbetween the control and the PTFE sample over the range of downforcetested. For the ceria slurry, a higher COF was observed for both controland the PTFE sample. At higher downforce, no significant differences inCOF were observed, indicating that the PTFE pad additive did not act asa lubricant. While the PTFE sample had a near-constant COF over theentire range of downforce tested, the control pad showed a rise in COFat downforce below 2 psi (13.8 kPa). The difference was attributed tothe lower roughness observed for the PTFE-containing pad.

Another test was conducted to gain insight into the effects offluoropolymer additions on the conditioning process. In this test aBuehler tabletop polisher was used to simulate the effects of theconditioning process. Pad samples were mounted and conditioned with aSaesol AK45 conditioner disk that was used at 101b force (4.5 kgf) withdeionized water to simulate the effects of pad break-in. Effluentsamples were taken at the beginning and end of the break-in cycle, andparticle size distribution was measured with an Accusizer particleanalysis tool. As shown in FIG. 3, a significant reduction in the paddebris size distribution was observed for both PTFE- and PFA-containingpads relative to the control pad. The most significant size reductionoccurred for particles in the 1-10 micron range. This was consistentwith the reduction in scratch defects when the two fluoropolymers wereadded to the parent pad.

While the tests outlined above can explain an aspect of the defectivityimprovements of the present invention, it did not shed light on theobserved increases in polishing rate. Accordingly, additional tests wereconducted.

The interactions between ceria (cerium oxide) and the fluoropolymeradditives used in the pad samples were probed using quartz crystalmicro-balance (QCM) measurements. During the QCM measurement, dilutedispersions of PTFE and PFA particles in deionized water (pH 6) werepassed through a flow cell containing a ceria crystal. Adsorption ofparticles on ceria crystal was demonstrated by increase in mass measuredby a sensitive micro-balance. As shown in FIG. 4, attractiveinteractions between ceria crystal and PTFE/PFA particles of severaldifferent sizes were observed. Since the zeta potential of the ceriacrystal at the test pH was positive, results indicate that thefluoropolymer particles have a negative zeta potential. This indicatedan extremely high negative zeta potential, which is driven by thehydrophobic surface and its effect on the water dipole orientation. Thiseffect is very different from the (negative) zeta potential ofpolyurethanes, which is driven by the structural hydroxyl groups presentin the polymer chain.

Conclusions from this test and the other data presented is that thepresence of the fluoropolymer particles at the pad surface helps toincrease polishing rate by increasing the overall attraction of ceriaparticles to the pad surface and, therefore raising the overall numberof particle/wafer interactions per unit time during polishing. Thiseffect does not occur when negatively charged silica particles are usedin slurries, as the electrostatic repulsion prevents a desirably highsurface concentration of particles from occurring.

In addition, the stability of the slurries was evaluated using aLumisizer dispersion analyzer settling study. The dispersion analyzeroperated in accordance with ISO/TR 1309, ISO/TR 18811, ISO18747-1 andISO13318-2. Sample of slurries with and without fluoropolymer additiveswere centrifuged with the transmission of light through the samplemeasured to determine how quickly the slurry particles settled. Thisbeing a measure of the stability of the slurries and thus aggregation.The slopes of the measurements with 0.1 wt % additive and without areshown in Table 3. If the fluoropolymer particles do not wet, then itbecomes necessary to a minimal amount of surfactant as necessary to wetthe particles, such as Merpol™ A alcohol phosphate nonionic surfactantfrom Stepan Company, to render the particles water soluble.

TABLE 3 Dispersion Data Sample Slope (%/hour) DANano control 296 Asahicontrol 622 SS25 control 14 DANano w/PTFE 285 DANano w/PFA 290 Asahiw/PTFE 601 Asahi w/PFA 601 SS25 w/PTFE 9 SS25 w/PFA 9

The slopes for samples with additives were consistently lower than thosewithout, indicating that they settle more slowly and were thus, morestable. This indicated that a reduction in defect could also originatefrom preventing ceria particle agglomeration for ceria particlecontaining slurries, such as DANano and Asahi. The relative stability ofsilica slurries, such as SS25 may explain the limited defectivityimprovement seen with fluoropolymer additives as ceria is moresusceptible to aggregation.

Example 4

To further illustrate the role of fluoropolymer additions on theproperties of the pad surface during polishing, a series of pads wereprepared using low-porosity polyurethane of Sample C as the base withvarying additions of PTFE-2 particles. Samples of each were polishedusing the process and slurry described in Example 3. Following thepolishing tests, polished samples of each pad were analyzed via X-rayPhotoelectron Spectroscopy (XPS) and Energy-Dispersive X-raySpectroscopy (EDS), to obtain compositional information on the effectsof polishing. XPS has a surface penetration depth of ˜1-10 nm, making itan extremely sensitive method of determining the composition of thesurface region, while EDS has a penetration depth of ˜1-10 um, whichgives information about the bulk concentration.

TABLE 4 XPS EDS PTFE % F (atom %) F/C F (atom %) F/C 0% 0 0 2% 25.5 0.253 0.045 5% 37.7 0.74 6.8 0.1 10%  45.5 1 8.3 0.132

As shown in Table 4, the surface of the used pads containingfluoropolymer showed substantial enrichment of fluorine at the outersurface relative to the bulk. This is strong evidence for the existenceof a fluorocarbon film on the pad surface during polishing.

Example 5

To obtain more information on the characteristics of the polished padsurface layer of the inventive pads, polishing tests were performed on acontrol pad and an inventive pad containing 10 wt % PTFE. The overallprocess and slurry described in Example 3 using the polishing pad ofExample 4. For this test, three different conditioners were used toassess their effects on polishing rate and texture. Conditioner AB45 wasa conditioner developed for use with ceria slurries, which produces alow roughness pad surface. Conditioner AK45 is a more aggressiveconditioner with larger diamonds at a higher density. Conditioner LPX-V1is a very aggressive conditioner employing a combination of large andsmall diamonds. After polishing, the surface textures of the used padswere examined using a NanoFocus non-contact laser profilometer.

FIG. 5A shows TEOS removal rates for the prior art control pad for eachof the three conditioners tested at three different polishing pressures(2, 3, and 4 psi, 13.8, 20.7 and 27.6 kPa). The low roughnessconditioner produced the highest removal rate, with little difference inrate effect for the other two conditioners. For the inventive pad (FIG.5B) polishing rates for all three conditioners were significantly higherfor all three conditioners, relative to the control.

Profilometry measurements were performed at the mid-point of thepolishing area using a Nano-focus confocal 3D surface metrology tool. Acomparison of the Root Mean Square (rms) roughness, measured inaccordance with ISO 25178, for each pad and conditioner is shown in FIG.6. For the prior art control pad, RMS roughness increased directly withconditioner aggressiveness. In contrast, the RMS roughness of theinventive pad was significantly lower for all conditioners.

Example 6

To further illustrate the criticality of zeta potential on rate forfluoropolymer additions, pads prepared with particle additions of PVFwere assessed for zeta potential and polishing performance with the samesilica-based and ceria-based commercial slurries used in Example 3. Asshown in Table 5 below, the zeta potentials for the additives used inpads of Example 3 and nitrogen-terminated PVF are quite different.

TABLE 5 Zeta potentials of fluoropolymer powders Sample Zeta Potential(mV) PTFE in water −36.3 PFA in water −47.3 PVF in water 33.6

The zeta potentials of PTFE and PFA were highly negative, while that ofthe PVF used was strongly positive. The addition of the cationic PVF toa pad of the present invention produced a heterogeneous surfacecontaining regions of positive and negative surface charge. Despite theoverall pad surface being electronegative, the resulting pad surfaceprovided attraction of slurry particles with a negative charge, such ascolloidal silica with a corresponding increase in polishing rate.Likewise, charge repulsion to slurry particles with a positive charge,such as ceria, in a slurry whose pH is below the isoelectric pH of theparticle, produced a reduced removal rate due to the reduce area ofattraction on the pad surface and the corresponding reduction in activeslurry particles on the pad contact surface.

Accordingly, a comparative polishing test was conducted using samples ofa low-porosity polyurethane polishing pad of Sample C, with and withouta 10 wt % addition of PVF during sample manufacturing. These pads wereused to polish TEOS wafers using conditions identical to those used inExample 3.

TABLE 6 Removal rate (Å/min) Slurry C + 10 wt % Comparison Slurry TypeControl C PVF to Control SS25 Silica 1656 1912 15% higher DANanoSTI12100F Ceria 1650 799 52% lower

As can be seen in Table 6, the polishing rate results showed theopposite trend to Example 4, i.e., the pad of the current invention withthe cationic additive enhanced the rate of the negatively charged silicaslurry, while the rate when used with a slurry with a positively chargedparticle was reduced.

The polymer-polymer composite polishing pads of the invention provide anunexpected large increase in polishing removal rate with a largedecrease in polishing defects. A relatively small amount offluoropolymer particle covers less than the entire surface to increasepolishing efficiency without compromising the polishing pad'shydrophilic surface required for efficient slurry distribution.

We claim:
 1. A method for polishing or planarizing a substrate of atleast one of semiconductor, optical and magnetic substrates, the methodcomprising the following: attaching a polymer-polymer compositepolishing pad to a polishing device, the polymer-polymer compositepolishing pad comprising a polishing layer having a polishing surfacefor polishing or planarizing the substrate; a polymeric matrix formingthe polishing layer, the polymer matrix having a tensile strength, andfluoropolymer particles embedded in the polymeric matrix, thefluoropolymer particles having a tensile strength lower than the tensilestrength of the polymeric matrix; applying a slurry to thepolymer-polymer composite polishing pad, the slurry containing cationicparticles; conditioning the polymer-polymer composite polishing pad withan abrasive to cut the polymer-polymer composite polishing pad; andrubbing the cut polymer-polymer composite polishing pad against thesubstrate to form the polishing surface having a fluorine concentrationmeasured by x-ray photoelectron spectroscopy in atomic percent at apenetration depth of 1 to 10 nm of at least ten percent higher than thebulk fluorine concentration measured with energy-dispersion X-rayspectroscopy at a penetration depth of 1 to 10 μm and to polish orplanarize the substrate with the thin film on the polishing surface. 2.The polishing or planarizing method of claim 1 wherein the slurryincludes abrasive particles having a positive zeta potential andpolishing or planarizing occurs with the fluoropolymer particles havinga zeta potential that is more negative than the polymer matrix.
 3. Thepolishing or planarizing method of claim 1 wherein the polishing orplanarizing occurs with the slurry containing ceria particles and at apH below the isoelectric pH of the ceria particles to increase substrateremoval rate.
 4. The polishing or planarizing method of claim 1 whereinthe polishing or planarizing occurs with the slurry containing ceriaparticles and at a pH below the isoelectric pH of the ceria particles todecrease polishing defects.
 5. The polishing or planarizing method ofclaim 1 wherein the polishing or planarizing occurs with a cationicslurry where the fluoropolymer increases friction between thepolymer-polymer composite polishing pad and the substrate to increasesubstrate removal rate.
 6. A method for polishing or planarizing asubstrate of at least one of semiconductor, optical and magneticsubstrates, the method comprising the following: attaching apolymer-polymer composite polishing pad to a polishing device, thepolymer-polymer composite polishing pad comprising a polishing layerhaving a polishing surface for polishing or planarizing the substrate, apolymeric matrix forming the polishing layer, the polymer matrix havinga tensile strength, and fluoropolymer embedded in the polymeric matrixthe fluoropolymer particles having a tensile strength lower than thetensile strength of the polymeric matrix; applying a slurry to thepolymer-polymer composite polishing pad, the slurry containing cationicparticles, the slurry including cationic particles; conditioning thepolymer-polymer composite polishing pad with an abrasive to cut thepolymer-polymer composite polishing pad; and rubbing the cutpolymer-polymer composite polishing pad against the substrate to formthe polishing surface having a fluorine concentration measured by x-rayphotoelectron spectroscopy in atomic percent at a penetration depth of 1to 10 nm of at least twenty percent higher than the bulk fluorineconcentration measured with energy-dispersion X-ray spectroscopy at apenetration depth of 1 to 10 μm and to polish or planarize the substratewith the thin film on the polishing surface.
 7. The polishing orplanarizing method of claim 6 wherein the slurry includes abrasiveparticles having a positive zeta potential and polishing or planarizingoccurs with the fluoropolymer particles having a zeta potential that ismore negative than the polymer matrix.
 8. The polishing or planarizingmethod of claim 6 wherein the polishing or planarizing occurs with theslurry containing ceria particles and at a pH below the isoelectric pHof the ceria particles to increase substrate removal rate.
 9. Thepolishing or planarizing method of claim 6 wherein the polishing orplanarizing occurs with the slurry containing ceria particles and at apH below the isoelectric pH of the ceria particles to decrease polishingdefects.
 10. The polishing or planarizing method of claim 6 wherein thepolishing or planarizing occurs with a cationic slurry where thefluoropolymer increases friction between the polymer-polymer compositepolishing pad and the substrate to increase substrate removal rate.